WO2000047654A1 - Highly resistant polymeric resin - Google Patents

Highly resistant polymeric resin Download PDF

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Publication number
WO2000047654A1
WO2000047654A1 PCT/DE2000/000381 DE0000381W WO0047654A1 WO 2000047654 A1 WO2000047654 A1 WO 2000047654A1 DE 0000381 W DE0000381 W DE 0000381W WO 0047654 A1 WO0047654 A1 WO 0047654A1
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Prior art keywords
polymer resin
resin
dendrimers
resin according
adhesive
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PCT/DE2000/000381
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German (de)
French (fr)
Inventor
Andreas Mittelbach
Georg Christian Wachinger
Klaus Schmidtke
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Daimlerchrysler Ag
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Publication of WO2000047654A1 publication Critical patent/WO2000047654A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Definitions

  • It relates to a high-strength polymer resin.
  • High-strength polymer resins such as in particular epoxy, polyurethane, or cyanate
  • Polyester resins are preferably used as adhesives or as matrix resins for the production of fiber-reinforced polymer resin laminates.
  • certain substances include, in particular, substances that reduce the brittleness of the polymer resin (Toughener).
  • Teoughener substances that reduce the brittleness of the polymer resin
  • the addition of one or more modifiers generally leads to an increase in toughness.
  • the object of the invention is to provide an improved high-strength polymer resin.
  • the high-strength polymer resin according to the invention is characterized in that the polymer resin contains dendrimers.
  • the polymer resin according to the invention has the advantage that it has high toughness (crash or impact performance) in the cured state, without other properties of the polymer resin such as viscosity, processability and aging behavior deteriorating appreciably. Another advantage is that the dendrimers used have good solubility in the resin compared to other modifiers commonly used.
  • the polymer resin advantageously contains 10 to 60% by weight, preferably 15 to 40% by weight, of dendrimers.
  • the polymer resin is preferably an epoxy, polyurethane, cyanate or polyester resin.
  • the dendrimers have a molecular weight of> 2000 AU.
  • a polymer resin with dendrimers which have a molecular weight of> 2000 AU is particularly, but not exclusively, suitable for use as a matrix resin for producing a fiber-reinforced polymer resin laminate.
  • the high glass transition area of the polymer resin according to the invention is particularly advantageous here.
  • Glass, carbon, aramid or natural fibers can be used as fibers for the production of the polymer resin laminate.
  • the dendrimers have a molecular weight of> 3000 AU.
  • a polymer resin according to the invention in which the dendrimers have a molecular weight of> 3000 AU is particularly, but not exclusively, suitable as a polymer resin for producing an adhesive.
  • the good corrosion resistance of the adhesive and the part surface of the polymer resin according to the invention covered with it and its ability to absorb or displace oil in the case of oiled surfaces are particularly important.
  • the polymer resin according to the invention is suitable as an adhesive for the connection of metal surfaces, as mentioned, in particular of oiled metal surfaces or generally for the production of an adhesive connection on such metal surfaces.
  • this adhesive however, not only metal surfaces but also glass, plastic, carbon fibers and ceramics can be glued.
  • a laminate test specimen (eg 40% resin mixture, 60% fiber, glass, carbon, aramid, natural fiber or the like) is produced from this mixture as an impact test specimen and tested with an impact bolt (standard bolt) with an energy of 10 J. Furthermore, a comparative test specimen was produced from unmodified resin. In the comparative test specimen made from unmodified resin, the damage area is 8 cm 2 , but in the test specimen made from modified resin according to the invention it is less than 0.2 cm 2 .
  • a suitable change of aromatic rings (hard area) and aliphatic chains / rings (soft area) in dendrimer molecules significantly improves the properties of the matrix resin with regard to impact stress, toughness and aging behavior.
  • Molecular weights of the dendrimer compounds of> 3000 AU are aimed for.
  • the molecules react completely via several reactive groups in the Polymer matrix. This ensures optimal integration into the resin matrix.
  • the resin matrix is largely stabilized by forming a three-dimensional network with many covalent bonds.
  • epoxy, polyurethane, cyanate or polyester resins are possible as the base resin.
  • a suitable choice of the three-dimensional structure of the dendrimer molecule and the design of the individual chains make it possible to achieve an optimal coordination between mechanical stability and anchoring in the polymer composite.
  • the large number of reactive groups and the relatively free choice of these groups ensure optimal integration into the polymer matrix (single-phase). This single-phase ensures that the mechanical properties of the resin-modifier composite are retained.
  • a high glass transition area can be set with the resin modified according to the invention.
  • a relatively low molecular weight of the dendrimer molecules to be used ensures good solubility of the modifier in the resin. There is no need to use solvents that are difficult to remove. Too much increase in
  • Viscosity is avoided, which considerably facilitates the processability of the resin system.
  • test specimens produced with the modified resin according to the invention can be improved by a factor of 2 to 10 in the tests carried out. Furthermore, with the modified resin according to the invention it is possible without difficulty to glue test specimens with a high degree of oiling. These also showed very good adhesion of the adhesive to the metal surfaces of the test specimens. In addition, the aging behavior was checked using a 1000 h salt spray test, 10 cycles of modified VDA test and three weeks of cataplasma test. No corrosive infiltration of the adhesive and / or the metal surface was found in any of the tests.
  • a suitable change of aromatic rings (hard area) and aliphatic chains / rings (soft area) in dendrimer molecules improve the adhesive properties with regard to crash stress, oil absorption and
  • the three-dimensional structure of the dendrimer molecule and the design of the individual chains make it possible to achieve an optimal coordination between mechanical stability and anchoring in the polymer composite.
  • the large number of reactive groups and the relatively free choice of these groups represents an optimal one
  • the adhesive bond Due to the better surface connection (adhesion) and by avoiding corrosive reactive groups, the adhesive bond is additionally protected against corrosive attacks.
  • the resin matrix is also stabilized against corrosive / hydrolytic influences through the integration of the dendrimer via a large number of covalent bonds.
  • high-strength polymer resins modified with dendrimers which have significantly improved properties with regard to impact stress, toughness and aging behavior and with regard to crash stress, oil absorption and corrosion stability.
  • These resins are particularly suitable as matrix resins for the production of fiber-reinforced polymer resin laminates and as high-strength adhesives, in particular for bonding metals. Even very oiled metal surfaces can be glued with very good adhesion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

According to the invention, a highly resistant polymeric resin modified with dendrimers is produced. The modified polymeric resin exhibits substantially improved properties in terms of impact resistance, tenacity, ageing performance, crash resistance, oil absorption and corrosion stability and is particularly suitable as matrix resin for the production of fiber-reinforced polymeric resin laminates or as a high-resistance adhesive. Said resin makes it possible to glue even heavily oiled metal surfaces without any problems.

Description

HOCHFESTES POLYMERHARZ HIGH-STRENGTH POLYMER RESIN
Die Er indung betrifft ein hochfestes Polymerharz.It relates to a high-strength polymer resin.
Hochfeste Polymerharze, wie insbesondere Epoxid-, Polyurethan-, Cyanat- oderHigh-strength polymer resins, such as in particular epoxy, polyurethane, or cyanate
Polyesterharze werden vorzugsweise als Kleber oder als Matrixharze zur Herstellung von faserverstärkten Polymerharzlaminaten verwendet. Zur Verbesserung der spezifischen Eigenschaften solcher Polymerharze werden diesen bestimmte Substanzen (Modifier) zugesetzt. Dazu zählen insbesondere Substanzen, die dem Polymerharz die Sprödigkeit nehmen (Toughener). Mit derartigen Zusätzen ist es jedoch nur bedingt möglich, die mechanischen Eigenschaften des Polymerharzes positiv zu beeinflussen, ohne auch gleichzeitig negative Wirkungen hervorzurufen, wie etwa größere Korrosionsanfälligkeit oder schlechtere Adhäsion im Falle eines Klebstoffs oder höhere Viskosität -und somit schlechtere Verarbeitbarkeit- oder schlechteres Alterungsverhalten im Falle eines Matrixharzes. So führt generell der Zusatz eines oder mehrerer Modifier zu einem Anstieg der Zähigkeit (Toughness). Andererseits sinkt dadurch die Steifigkeit und der Glasübergangsbereich und es kann die Wasseraufnahme mit einer Gefahr von hydrolytischer Bindungsspaltung ansteigen und im Falle höherer Molekulargewichte der Modifier hat der Verbund Harz-Modifier eine Tendenz zur Bildung eines zweiphasigen Gemisches, wodurch die mechanische Leistungsfähigkeit des Harzes nicht voll entfaltet wird.Polyester resins are preferably used as adhesives or as matrix resins for the production of fiber-reinforced polymer resin laminates. To improve the specific properties of such polymer resins, certain substances (modifiers) are added to them. These include, in particular, substances that reduce the brittleness of the polymer resin (Toughener). With such additives, however, it is only possible to a limited extent to influence the mechanical properties of the polymer resin positively, without at the same time causing negative effects, such as greater susceptibility to corrosion or poorer adhesion in the case of an adhesive or higher viscosity - and thus poorer processability - or poorer aging behavior in the Case of a matrix resin. The addition of one or more modifiers generally leads to an increase in toughness. On the other hand, this reduces the rigidity and the glass transition area and the water absorption can increase with a risk of hydrolytic bond cleavage and in the case of higher molecular weights of the modifiers, the composite resin modifier tends to form a two-phase mixture, which means that the mechanical performance of the resin is not fully developed becomes.
Die Aufgabe der Erfindung ist es, ein verbessertes hochfestes Polymerharz zu schaffen.The object of the invention is to provide an improved high-strength polymer resin.
Diese Aufgabe wird durch das im Anspruch 1 angegebene hochfeste Polymerharz gelöst.This object is achieved by the high-strength polymer resin specified in claim 1.
Vorteilhafte Ausgestaltungen des erfindungsgemäßen Polymerharzes sind in den Unteransprüchen gekennzeichnet.Advantageous embodiments of the polymer resin according to the invention are characterized in the subclaims.
Das erfindungsgemäße hochfeste Polymerharz ist dadurch gekennzeichnet, daß das Polymerharz Dendrimere enthält. Das erfindungsgemäße Polymerharz hat den Vorteil, daß es im ausgehärteten Zustand eine hohe Zähigkeit (Crash- oder Impactperformance) aufweist, ohne daß sich andere Eigenschaften des Polymerharzes wie Viskosität, Verarbeitbarkeit und Alterungsverhalten nennenswert verschlechtert. Ein weiterer Vorteil ist es, daß die verwendeten Dendrimere gegenüber anderen üblicherweise verwendeten Modifiern eine gute Löslichkeit im Harz aufweisen.The high-strength polymer resin according to the invention is characterized in that the polymer resin contains dendrimers. The polymer resin according to the invention has the advantage that it has high toughness (crash or impact performance) in the cured state, without other properties of the polymer resin such as viscosity, processability and aging behavior deteriorating appreciably. Another advantage is that the dendrimers used have good solubility in the resin compared to other modifiers commonly used.
Vorteilhafterweise enthält das Polymerharz 10 bis 60 Gew.-%, vorzugsweise 15 bis 40 Gew.-% Dendrimere.The polymer resin advantageously contains 10 to 60% by weight, preferably 15 to 40% by weight, of dendrimers.
Vorzugsweise ist das Polymerharz ein Epoxid-, Polyurethan-, Cyanat- oder Polyesterharz.The polymer resin is preferably an epoxy, polyurethane, cyanate or polyester resin.
Vorteilhafterweise sind die Dendrimere mit einer oder mehreren der folgenden Verbindungen als Endgruppen versehen: Oxiranring, -OH, -SH, -NHx (X = 1, 2), -COOH, - Allyl, -Anhydrid.The dendrimers are advantageously provided with one or more of the following compounds as end groups: oxirane ring, -OH, -SH, -NHx (X = 1, 2), -COOH, - allyl, anhydride.
Gemäß einer bevorzugten Ausführungsform der Erfindung haben die Dendrimere ein Molekulargewicht von > 2000 AU.According to a preferred embodiment of the invention, the dendrimers have a molecular weight of> 2000 AU.
Ein Polymerharz mit Dendrimeren, die ein Molekulargewicht von > 2000 AU aufweisen, ist insbesondere, jedoch nicht ausschließlich, zur Verwendung als Matrixharz zur Herstellung eines faserverstärkten Polymerharzlaminats geeignet. Hierbei kommt vorteilhafterweise insbesondere der hohe Glasübergangsbereich des erfindungsgemäßen Polymerharzes zum Tragen.A polymer resin with dendrimers which have a molecular weight of> 2000 AU is particularly, but not exclusively, suitable for use as a matrix resin for producing a fiber-reinforced polymer resin laminate. The high glass transition area of the polymer resin according to the invention is particularly advantageous here.
Als Fasern zur Herstellung des Polymerharzlaminats können Glas-, Carbon-, Aramid- oder Naturfasern verwendet werden.Glass, carbon, aramid or natural fibers can be used as fibers for the production of the polymer resin laminate.
Gemäß einer anderen bevorzugten Ausführungsform der Erfindung ist es vorgesehen, daß die Dendrimere ein Molekulargewicht von > 3000 AU aufweisen. Ein erfindungsgemäßes Polymerharz, bei dem die Dendrimere ein Molekulargewicht von >3000 AU aufweisen, ist insbesondere, jedoch nicht ausschließlich als Polymerharz zur Herstellung eines Klebstoffs geeignet. Hierbei kommt insbesondere die gute Korrosionsbeständigkeit des Klebstoffs und der damit bedeckten Fügeteiloberfläche des erfindungsgemäßen Polymerharzes und dessen Fähigkeit zur Ölabsorption oder Ölverdrängung im Falle von beölten Oberflächen zum Tragen.According to another preferred embodiment of the invention, it is provided that the dendrimers have a molecular weight of> 3000 AU. A polymer resin according to the invention in which the dendrimers have a molecular weight of> 3000 AU is particularly, but not exclusively, suitable as a polymer resin for producing an adhesive. The good corrosion resistance of the adhesive and the part surface of the polymer resin according to the invention covered with it and its ability to absorb or displace oil in the case of oiled surfaces are particularly important.
Insbesondere ist das erfindungsgemäße Polymerharz als Klebstoff zur Verbindung von Metalloberflächen, wie erwähnt, insbesondere von beölten Metalloberflächen oder allgemein zur Herstellung einer Klebeverbindung auf derartigen Metalloberflächen geeignet. Mit diesem Klebstoff können jedoch nicht nur Metalloberflächen sondern auch Glas, Kunststoff, Carbonfasern und Keramiken verklebt werden.In particular, the polymer resin according to the invention is suitable as an adhesive for the connection of metal surfaces, as mentioned, in particular of oiled metal surfaces or generally for the production of an adhesive connection on such metal surfaces. With this adhesive, however, not only metal surfaces but also glass, plastic, carbon fibers and ceramics can be glued.
Im folgenden soll die Erfindung anhand von Ausführungsbeispielen beschrieben werden.In the following, the invention will be described using exemplary embodiments.
AUSFUHRUNGSBEISPIELEXAMPLE OF EXAMPLE
140 g DGEBA werden bei 60°C aufgeschmolzen und darin 40 g mit Epichlorhydrin epoximodifiziertes Starburst (PAMAM) Dendrimer G4 und 7 g Dicyandiamid eingerührt. Aus dieser Mischung wird ein Laminatprüfkörper (z.B. 40 % Harzmischung, 60 % Faser, Glas-, Carbon-, Aramid-, Naturfaser o.a.) als Impactprüfkörper hergestellt und mit einem Impactbolzen (Standardbolzen) mit einer Energie von 10 J geprüft. Weiterhin wurde ein Vergleichsprüfkörper aus unmodifiziertem Harz hergestellt. Bei dem aus unmodifiziertem Harz hergestellten Vergleichsprüfkörper ist die Schadensfläche 8 cm2, bei dem aus erfindungsgemäßem, modifiziertem Harz hergestellten Prüfkörper jedoch kleiner als 0,2 cm2.140 g of DGEBA are melted at 60 ° C. and 40 g of Starburst (PAMAM) dendrimer G4 epoxy-modified with epichlorohydrin and 7 g of dicyandiamide are stirred therein. A laminate test specimen (eg 40% resin mixture, 60% fiber, glass, carbon, aramid, natural fiber or the like) is produced from this mixture as an impact test specimen and tested with an impact bolt (standard bolt) with an energy of 10 J. Furthermore, a comparative test specimen was produced from unmodified resin. In the comparative test specimen made from unmodified resin, the damage area is 8 cm 2 , but in the test specimen made from modified resin according to the invention it is less than 0.2 cm 2 .
Durch einen geeigneten Wechsel von aromatischen Ringen (Hartbereich) und aliphatischen Ketten/Ringen (Weichbereich) in Dendrimermolekülen verbessern sich die Eigenschaften des Matrixharzes hinsichtlich Impactbeanspruchung, Zähigkeit und Alterungsverhalten wesentlich. Es werden Molekulargewichte der Dendrimerverbindungen von > 3000 AU angestrebt. Die Moleküle reagieren vollständig über mehrere reaktive Gruppen in die Polymermatrix. Dadurch wird eine optimale Einbindung in die Harzmatrix gewährleistet. Die Harzmatrix wird durch Ausbildung eines dreidimensionalen Netzwerks mit vielen kovalenten Bindungen weitgehend stabilisiert. Als Basisharz sind z.B. Epoxid-, Polyurethan-, Cyanat- oder Polyesterharze möglich.A suitable change of aromatic rings (hard area) and aliphatic chains / rings (soft area) in dendrimer molecules significantly improves the properties of the matrix resin with regard to impact stress, toughness and aging behavior. Molecular weights of the dendrimer compounds of> 3000 AU are aimed for. The molecules react completely via several reactive groups in the Polymer matrix. This ensures optimal integration into the resin matrix. The resin matrix is largely stabilized by forming a three-dimensional network with many covalent bonds. For example, epoxy, polyurethane, cyanate or polyester resins are possible as the base resin.
Durch eine geeignete Wahl der dreidimensionalen Struktur des Dendrimermoleküls und die Gestaltung der einzelnen Ketten ist es möglich, eine optimale Abstimmung zwischen mechanischer Stabilität und Verankerung im Polymerverbund zu verwirklichen. Die große Zahl an reaktiven Gruppen und die relativ freie Wahl dieser Gruppen stellt eine optimale Einbindung in die Polymermatrix sicher (Einphasigkeit). Diese Einphasigkeit sichert einen Erhalt der mechanischen Eigenschaften des Harz-Modifier-Verbundes. Mit dem erfindungsgemäß modifizierten Harz läßt sich ein hoher Glasübergangsbereich einstellen.A suitable choice of the three-dimensional structure of the dendrimer molecule and the design of the individual chains make it possible to achieve an optimal coordination between mechanical stability and anchoring in the polymer composite. The large number of reactive groups and the relatively free choice of these groups ensure optimal integration into the polymer matrix (single-phase). This single-phase ensures that the mechanical properties of the resin-modifier composite are retained. A high glass transition area can be set with the resin modified according to the invention.
Dendrimere lassen sich mit unterschiedlichen Endgruppen versehen und somit an spezielle Anforderungen anpassen. Als mögliche Gruppen kommen in Frage: Oxiranring, - OH, -SH, -NHx (X = 1, 2), -COOH, -Allyl, -Anhydrid o.a..Dendrimers can be provided with different end groups and thus adapted to special requirements. Possible groups are: oxirane ring, OH, SH, NHx (X = 1, 2), COOH, allyl, anhydride or the like.
Durch ein relativ geringes Molekulargewicht der einzusetzenden Dendrimermoleküle ist eine gute Löslichkeit des Modifiers im Harz gewährleistet. Auf den Einsatz von nur schwer zu entfernenden Lösungsmitteln kann verzichtet werden. Ein zu starker Anstieg derA relatively low molecular weight of the dendrimer molecules to be used ensures good solubility of the modifier in the resin. There is no need to use solvents that are difficult to remove. Too much increase in
Viskosität wird vermieden, was die Verarbeitbarkeit des Harzsystems erheblich erleichtert.Viscosity is avoided, which considerably facilitates the processability of the resin system.
AUSFÜHRUNGSBEISPIELEXAMPLE EXAMPLE
140 g DGEBA werden bei 60°C aufgeschmolzen und darin 60 g mit Epichlorhydrin epoximodifiziertes Starburst (PAMAM) Dendrimer G4 und 7 g Dicyandiamid eingerührt. Mit dieser Mischung werden standardisierte Prüfkörper (Schubspannung-Gleitungs-Prüfkörper und Crashprüfkörper) verklebt und geprüft. Weiterhin werden mit unmodifiziertem Harz verklebte Vergleichsprüfkörper hergestellt. Bei den mit dem erfindungsgemäßen, modifizierten Harz hergestellten Prüfkörpern lassen sich bei den durchgeführten Tests Verbesserungen um den Faktor 2 bis 10 erreichen. Weiterhin ist es mit dem erfindungsgemäßen, modifizierten Harz ohne Schwierigkeiten möglich, Prüfkörper mit einem hohen Beölungsgrad zu verkleben. Auch diese zeigten eine sehr gute Adhäsion des Klebers an den Metalloberflächen der Prüfkörper. Weiterhin wurde das Alterungsverhalten mit 1000 h Salzsprühtest, 10 Zyklen modifiziertem VDA-Test und drei Wochen Kataplasmatest überprüft. Bei keinem der Tests wurde eine korrosive Unterwanderung des Klebstoffs und/oder der Metalloberfläche festgestellt.140 g of DGEBA are melted at 60 ° C. and 60 g of Starburst (PAMAM) dendrimer G4 epoxy-modified with epichlorohydrin and 7 g of dicyandiamide are stirred therein. Standardized test specimens (shear stress-sliding test specimen and crash test specimen) are bonded and tested with this mixture. Comparative test specimens bonded with unmodified resin are also produced. The test specimens produced with the modified resin according to the invention can be improved by a factor of 2 to 10 in the tests carried out. Furthermore, with the modified resin according to the invention it is possible without difficulty to glue test specimens with a high degree of oiling. These also showed very good adhesion of the adhesive to the metal surfaces of the test specimens. In addition, the aging behavior was checked using a 1000 h salt spray test, 10 cycles of modified VDA test and three weeks of cataplasma test. No corrosive infiltration of the adhesive and / or the metal surface was found in any of the tests.
Durch einen geeigneten Wechsel von aromatischen Ringen (Hartbereich) und aliphatischen Ketten/Ringen (Weichbereich) in Dendrimermolekülen verbessern sich die Klebstoffeigenschaften hinsichtlich Crashbeanspruchung, Ölabsorption undA suitable change of aromatic rings (hard area) and aliphatic chains / rings (soft area) in dendrimer molecules improve the adhesive properties with regard to crash stress, oil absorption and
Korrosionsstabilität wesentlich. Es werden Molekulargewichte der Dendrimerverbindungen von > 3000 AU angestrebt. Die Moleküle reagieren vollständig über mehrere reaktive Gruppen in die Polymermatrix. Dadurch wird eine optimale Einbindung in den Klebstoff gewährleistet. Die Klebstoffmatrix wird durch die Ausbildung eines dreidimensionalen Netzwerks mit vielen kovalenten Bindungen weitgehend stabilisiert.Corrosion stability essential. Molecular weights of the dendrimer compounds of> 3000 AU are aimed for. The molecules react completely via several reactive groups in the polymer matrix. This ensures optimal integration into the adhesive. The adhesive matrix is largely stabilized by the formation of a three-dimensional network with many covalent bonds.
Durch die dreidimensionale Struktur des Dendrimermoleküls und die Gestaltung der einzelnen Ketten ist es möglich, eine optimale Abstimmung zwischen mechanischer Stabilität und Verankerung im Polymerverbund zu verwirklichen. Die große Anzahl an reaktiven Gruppen und die relativ freie Wahl dieser Gruppen stellt eine optimaleThe three-dimensional structure of the dendrimer molecule and the design of the individual chains make it possible to achieve an optimal coordination between mechanical stability and anchoring in the polymer composite. The large number of reactive groups and the relatively free choice of these groups represents an optimal one
Einbindung in die Polymermatrix sicher (Einphasigkeit). Die Adhäsion des Klebstoffs auf unterschiedlichen, insbesondere metallischen Oberflächen wird nicht durch eine zu große Hydrophobität der Dendrimermoleküle herabgesetzt. Die somit verbesserte Anbindung des Klebers erhöht die mechanische Stabilität des Verbundes.Safe integration into the polymer matrix (single-phase). The adhesion of the adhesive to different, in particular metallic, surfaces is not reduced by the hydrophobicity of the dendrimer molecules being too great. The improved bonding of the adhesive thus increases the mechanical stability of the composite.
Durch die bessere Oberflächenanbindung (Adhäsion) und durch Vermeiden von korrosiv wirkenden reaktiven Gruppen wird der Klebeverbund zusätzlich gegen korrosive Angriffe geschützt. Die Harzmatrix wird durch die Einbindung des Dendrimers über eine Vielzahl kovalenter Bindungen auch gegen korrosive/hydrolytische Einflüsse stabilisiert.Due to the better surface connection (adhesion) and by avoiding corrosive reactive groups, the adhesive bond is additionally protected against corrosive attacks. The resin matrix is also stabilized against corrosive / hydrolytic influences through the integration of the dendrimer via a large number of covalent bonds.
Aufgrund der Molmasse, der Poren (freies Volumen) im Dendrimer und die spezielle Abstimmung der Dendrimerarme ist es möglich, auch auf beölten Oberflächen eine gute Adhäsion zu erreichen. Dabei wird das auf der Oberfläche vorhandene Öl entweder absorbiert oder es wird durch den Klebstoff bei der Oberflächenbenetzung verdrängt.Due to the molecular weight, the pores (free volume) in the dendrimer and the special adjustment of the dendrimer arms, it is possible to have a good one even on oiled surfaces To achieve adhesion. The oil on the surface is either absorbed or displaced by the adhesive during surface wetting.
Die bei der Herstellung des Polymerklebstoffs verwendeten Dendrimere lassen sich mit unterschiedlichen Endgruppen versehen und somit an spezielle Anforderungen anpassen. Als mögliche Gruppen kommen in Frage: Oxiranring, -OH, -SH, NHx (X = 1 , 2), -COOH, -Allyl, -Anhydrid o.a..The dendrimers used in the production of the polymer adhesive can be provided with different end groups and thus adapted to special requirements. Possible groups are: oxirane ring, -OH, -SH, NHx (X = 1, 2), -COOH, -allyl, -hydride or the like.
Gemäß der Erfindung ist es möglich, mit Dendrimeren modifizierte hochfeste Polymerharze zu schaffen, die hinsichtlich Impactbeanspruchung, Zähigkeit und Alterungsverhalten sowie hinsichtlich Crashbeanspruchung, Ölabsorption und Korrosionsstabilität wesentlich verbesserte Eigenschaften aufweisen. Diese Harze sind insbesondere als Matrixharze zur Herstellung von faserverstärkten Polymerharzlaminaten und als hochfeste Klebstoffe, insbesondere zum Verkleben von Metallen geeignet. Selbst das Verkleben von stark beölten Metalloberflächen ist mit sehr guter Adhäsion möglich. According to the invention, it is possible to create high-strength polymer resins modified with dendrimers which have significantly improved properties with regard to impact stress, toughness and aging behavior and with regard to crash stress, oil absorption and corrosion stability. These resins are particularly suitable as matrix resins for the production of fiber-reinforced polymer resin laminates and as high-strength adhesives, in particular for bonding metals. Even very oiled metal surfaces can be glued with very good adhesion.

Claims

Patentansprüche claims
1. Hochfestes Polymerharz, dadurch gekennzeichnet, daß das Polymerharz Dendrimere enthält.1. High-strength polymer resin, characterized in that the polymer resin contains dendrimers.
2 Polymerharz nach Anspruch 1 , dadurch gekennzeichnet, daß das Polymerharz 10 bis 60 Gew -%, vorzugsweise 15 bis 40 Gew.-% Dendrimere enthalt.2 polymer resin according to claim 1, characterized in that the polymer resin contains 10 to 60% by weight, preferably 15 to 40% by weight, of dendrimers.
3. Polymerharz nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Polymerharz ein Epoxid-, Polyurethan-, Cyanat- oder Polyesterharz ist.3. Polymer resin according to claim 1 or 2, characterized in that the polymer resin is an epoxy, polyurethane, cyanate or polyester resin.
4. Polymerharz nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß die Dendrimere eine oder mehrere der folgenden Verbindungen als Endgruppen aufweisen. Oxiranring, -OH, -SH, -NHx (X = 1 , 2), -COOH, -Allyl, -Anhydrid.4. Polymer resin according to claim 1, 2 or 3, characterized in that the dendrimers have one or more of the following compounds as end groups. Oxirane ring, -OH, -SH, -NHx (X = 1, 2), -COOH, -Allyl, -hydride.
5. Polymerharz nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Dendrimere ein Molekulargewicht von > 2000 AU aufweisen.5. Polymer resin according to one of claims 1 to 4, characterized in that the dendrimers have a molecular weight of> 2000 AU.
6. Polymerharz nach Anspruch 5, dadurch gekennzeichnet, daß das Polymerharz als Matrixharz zur Herstellung eines faserverstärkten Polymerharzlaminats verwendet wird.6. Polymer resin according to claim 5, characterized in that the polymer resin is used as a matrix resin for producing a fiber-reinforced polymer resin laminate.
7. Polymerharz nach Anspruch 6, dadurch gekennzeichnet, daß als Fasern zur Herstellung des Polymerharzlaminats Glas-, Carbon-, Aramid- oder Naturfasern verwendet werden7. Polymer resin according to claim 6, characterized in that glass, carbon, aramid or natural fibers are used as fibers for the production of the polymer resin laminate
8. Polymerharz nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Dendrimere ein Molekulargewicht von > 3000 AU aufweisen8. Polymer resin according to one of claims 1 to 4, characterized in that the dendrimers have a molecular weight of> 3000 AU
9. Polymerharz nach Anspruch 8, dadurch gekennzeichnet, daß das Polymerharz zur Herstellung eines Klebstoffs verwendet wird. 9. Polymer resin according to claim 8, characterized in that the polymer resin is used to produce an adhesive.
0. Polymerharz nach Anspruch 9, dadurch gekennzeichnet, daß der Klebstoff zur0. Polymer resin according to claim 9, characterized in that the adhesive for
Verbindung von Metalloberflächen, insbesondere von beölten Metalloberflächen dient.Connection of metal surfaces, in particular oiled metal surfaces.
1. Polymerharz nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Polymerharz zur Herstellung einer Klebeverbindung auf Metalloberflächen, insbesondere auf beölten Metalloberflächen dient. 1. Polymer resin according to one of claims 1 to 10, characterized in that the polymer resin is used to produce an adhesive bond on metal surfaces, in particular on oiled metal surfaces.
PCT/DE2000/000381 1999-02-12 2000-02-08 Highly resistant polymeric resin WO2000047654A1 (en)

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